US6818727B2 - Highly purified epoxy resin - Google Patents
Highly purified epoxy resin Download PDFInfo
- Publication number
- US6818727B2 US6818727B2 US09/320,719 US32071999A US6818727B2 US 6818727 B2 US6818727 B2 US 6818727B2 US 32071999 A US32071999 A US 32071999A US 6818727 B2 US6818727 B2 US 6818727B2
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- United States
- Prior art keywords
- epoxy resin
- hydrolyzable chlorine
- solution
- added
- ppm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- IBXPYDYSHCLAEU-UHFFFAOYSA-N CC1=CC=C(OCC(CCl)OCC2CO2)C=C1 Chemical compound CC1=CC=C(OCC(CCl)OCC2CO2)C=C1 IBXPYDYSHCLAEU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
Definitions
- the present invention relates to an epoxy resin containing low content of hydrolyzable chlorine, which is useful for adhesives, paints and electric/electronic materials(e.g. insulation materials, laminated plate, etc.).
- epoxy resins used for electric/electronic materials It is indispensable for epoxy resins used for electric/electronic materials that the content of hydrolyzable chlorine is low.
- typical epoxy resins such as bisphenol A type, bisphenol F type, and orthocresol novolak type epoxy resin
- purification has been conducted, and epoxy resins containing hydrolyzable chlorine of 500 ppm or less, and in a specially purified case, those containing hydrolyzable chlorine of about 200 ppm have been developed.
- epoxy resins having glycidylamino group especially aminophenol type epoxy resins such as 4-amino-m-cresol type and 4-aminophenol type epoxy resins, it has been rarely used for an electric/electronic material, and because of difficulty of the preparation, epoxy resins of high purity have not been developed, and the hydrolyzable chlorine content has been usually 1000 ppm or more.
- An object of the present invention is to provide an epoxy resin of low hydrolyzable chlorine content, which is highly reliable in the use for adhesives, paints and electric/electronic materials (e.g. insulation materials, laminated plate, etc.).
- the present invention is as follows.
- the epoxy resin having glycidylamino group in the present invention is an epoxy resin obtained by reacting various kinds of aminophenol with epihalohydrin, and epoxidizing.
- Concrete examples include an aminophenol type epoxy resin, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl metaxylenediamine, hexaglycidyl triaminobenzene, etc., without being limited thereto.
- the aminophenol type epoxy resin is epoxidation product of various kinds of aminophenol by a known method.
- aminophenols examples include aminophenols and aminocresols, such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-amino-m-cresol, 2-amino-p-cresol, 3-amino-o-cresol, 4-amino-m-cresol, and 6-amino-m-cresol, without being limited thereto.
- aminophenols and aminocresols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-amino-m-cresol, 2-amino-p-cresol, 3-amino-o-cresol, 4-amino-m-cresol, and 6-amino-m-cresol, without being limited thereto.
- Suitable viscosity of the epoxy resin having glycidylamino group is depends on the combination with a curing agent and an additive, and not especially limited, but generally it is desirable to be low. That is, when the viscosity of the epoxy resin combined with a curing agent and an additive is high, the coating property and immersing property become inferior and make the working properties bad.
- the viscosity of the epoxy resin having glycidylamino group is preferably 2000 Pas or less.
- the hydrolyzable chlorine means a chlorine contained in:
- the content of hydrolyzable chlorine is analyzed by the following method.
- the condenser is removed from the Erlenmeyer flask, and the sample liquid is transferred into a 200 mL beaker. Inside of the flask is washed three times with 80% acetone water (total 50 mL), and the washed liquid is added to the sample liquid.
- the content of hydrolyzable chlorine is calculated by the following formula.
- the preparation method of an epoxy resin having glycidylamino group, whose hydrolyzable chlorine content is 1000 ppm or less is not especially limited.
- the epoxy resin can be obtained by dechlorination and ring-closure reaction of an epoxy resin having glycidylamino group whose hydrolyzable chlorine content is more than 1000 ppm.
- Dechlorination reaction is carried out by dissolving an epoxy resin having glycidylamino group in non-protonic polar solvent, and an alkaline substance is added dropwise and retained with stirring.
- sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. are exemplified, and these are used in the form of aqueous solution or alcoholic solution.
- the amount of alkaline substance is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol based on 1 mol of the hydrolyzable chlorine of epoxy resin. When too much amount of alkaline substance is used, polymerization will occur, and when too little, the effect of reduction of hydrolyzable chlorine will become small.
- non-protonic polar solvent dimethylsulfoxide, dimethyl sulfone, dimethylacetamide, tetramethylurea, hexamethylphophoramide, etc. are raised, but it is not limited to these.
- the amount of non-protonic polar solvent can be used arbitrarily to the amount of epoxy resins, it is suitably 1.0 to 20 times in weight ratio.
- Ring-closure reaction is carried out as follows. From the reaction solution obtained above, non-protonic polar solvent contained therein is removed by water-washing or by distillation, and to the solution of the residue whose solvent is replaced with an organic solvent other than non-protonic polar solvent, alkaline substance is added dropwise and stirred, and after the reaction, neutralization is carried out. After then, purification is conducted by partition with water-washing or filtration.
- organic solvents other than non-protonic polar solvent used in ring-closure reaction various hydrocarbon solvents and ketone are exemplified, without being limited to these. Among them, ketones such as methylisobutylketone are suitable.
- the epoxy resin of the present invention can be used in combination with a curing agent, a curing accelerator, etc.
- a curing agent any curing agent which is usually used as a curing agent for epoxy resins can be used.
- the curing agent include dicyandiamide, tetramethylguanidine, polyhydric compounds, acid anhydrides, acid hydrazid compounds, aromatic amines, aliphatic amines and alicyclic amines.
- the epoxy resin of the present invention can be used, according to requirements, with adding fillers such as silica, alumina.
- Epoxy resin having glycidylamino group with low content of hydrolyzable chlorine of the present invention is useful as electric and electronic materials, such as adhesive, insulating material, and laminated board.
- Viscosity is measured with using a parallel plate type rheometer (CVO Rheometer, produced by Bohlin Co., Ltd.).
- 4-amino-m-cresol type epoxy resin having 1450 ppm of hydrolyzable chlorine (comparative example 1, trade name SumiEpoxy ELM-100, Sumitomo Chemical Co.,Ltd.) 60 g was dissolved in dimethylsulfoxide 440 g, and after having replaced the inside of the system with nitrogen, 48% sodium hydroxide aqueous solution 0.35 g (example 1) or 1.27 g (example 2) were added dropwise, respectively, and stirred at 32° C. for 2 hours. After the reaction, neutralization was carried out by adding 0.21 g of phosphoric acid, and 2.4 g of sodium chloride.
- Example 2 example 1 Charged amount 0.35 g 1.27 g — of 48% NaOH Hydrolyzable 830 ppm 660 ppm 1450 ppm chlorine Viscosity (25° C.) 1.7 Pas 4.0 Pas 1.1 Pas
- an epoxy resin having glycidylamino group with low content of hydrolyzable chlorine which is highly reliable and useful as electric/electronic materials can be provided.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Provided is an epoxy resin having glycidylamino group, wherein the content of hydrolyzable chlorine is 1000 ppm or less. The epoxy resin is useful for adhesives, paints and electric/electronic materials(e.g. insulation materials, laminated plate, etc.).
Description
1. Field of the Invention
The present invention relates to an epoxy resin containing low content of hydrolyzable chlorine, which is useful for adhesives, paints and electric/electronic materials(e.g. insulation materials, laminated plate, etc.).
2. Description of the Related Art
It is indispensable for epoxy resins used for electric/electronic materials that the content of hydrolyzable chlorine is low. As for typical epoxy resins, such as bisphenol A type, bisphenol F type, and orthocresol novolak type epoxy resin, purification has been conducted, and epoxy resins containing hydrolyzable chlorine of 500 ppm or less, and in a specially purified case, those containing hydrolyzable chlorine of about 200 ppm have been developed.
However, as for epoxy resins having glycidylamino group, especially aminophenol type epoxy resins such as 4-amino-m-cresol type and 4-aminophenol type epoxy resins, it has been rarely used for an electric/electronic material, and because of difficulty of the preparation, epoxy resins of high purity have not been developed, and the hydrolyzable chlorine content has been usually 1000 ppm or more.
An object of the present invention is to provide an epoxy resin of low hydrolyzable chlorine content, which is highly reliable in the use for adhesives, paints and electric/electronic materials (e.g. insulation materials, laminated plate, etc.).
The present invention is as follows.
(1) An epoxy resin having glycidylamino group, wherein the content of hydrolyzable chlorine as an impurity is 1000 ppm or less.
(2) The epoxy resin according to (1), wherein the epoxy resin having glycidylamino group is an aminophenol type epoxy resin.
(3) The epoxy resin according to (2), wherein the aminophenol type epoxy resin is a 4-amino-m-cresol type epoxy resin.
(4) The epoxy resin according to (2), wherein the aminophenol type epoxy resin is a 4-amino-phenol type epoxy resin.
The epoxy resin having glycidylamino group in the present invention is an epoxy resin obtained by reacting various kinds of aminophenol with epihalohydrin, and epoxidizing. Concrete examples include an aminophenol type epoxy resin, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl metaxylenediamine, hexaglycidyl triaminobenzene, etc., without being limited thereto.
In the present invention, the aminophenol type epoxy resin is epoxidation product of various kinds of aminophenol by a known method.
Examples of the aminophenol include aminophenols and aminocresols, such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-amino-m-cresol, 2-amino-p-cresol, 3-amino-o-cresol, 4-amino-m-cresol, and 6-amino-m-cresol, without being limited thereto.
Suitable viscosity of the epoxy resin having glycidylamino group is depends on the combination with a curing agent and an additive, and not especially limited, but generally it is desirable to be low. That is, when the viscosity of the epoxy resin combined with a curing agent and an additive is high, the coating property and immersing property become inferior and make the working properties bad. Thus the viscosity of the epoxy resin having glycidylamino group is preferably 2000 Pas or less.
In the present invention, the hydrolyzable chlorine means a chlorine contained in:
and not limited only to that contained in 1,2-chlorohydrin group.
In the present invention, the content of hydrolyzable chlorine is analyzed by the following method.
That is, about 1 g of a sample is accurately weighed to 1 mg unit in a 100 mL ground glass Erlenmeyer flask. Dioxane 30 mL is added and the sample is dissolved completely using an ultrasonic apparatus. After 5 mL of 1N potassium hydroxide/ethanol solution is added accurately and shaked, boiling tips are put in and a condenser is attached to the flask. It is refluxed on a sand bath with heating at about 180° C. Here the refluxing time is set to be correctly 30 minutes from the start of boiling. After cooling to room temperature, the condenser is washed by methanol 5 mL, and then the washed liquid is added to the sample liquid. The condenser is removed from the Erlenmeyer flask, and the sample liquid is transferred into a 200 mL beaker. Inside of the flask is washed three times with 80% acetone water (total 50 mL), and the washed liquid is added to the sample liquid.
To the sample liquid, N/400 sodium chloride solution 5 mL is added accurately, and a rotor is put in. After adding acetic acid 3 mL and stirring for 2 minutes, potentiometric titration is conducted according to the condition shown by the table 1 below, with using N/100 silver nitrate solution. The same operation as above is performed as a blank test.
TABLE 1 | |||
Potentiometric titration device, | |||
Device | (made by Metrom Co., Ltd.) | ||
Titration range | 750 mV FS | ||
Dropping velocity | 10 min/100% vol | ||
Auto control | 5 | ||
Selector switch | pH, mV | ||
Cylinder | 520 mL | ||
The content of hydrolyzable chlorine is calculated by the following formula.
In the formula:
F; Factor of the N/100 silver nitrate solution
V; Amount of the N/100 silver nitrate solution used for titration of the sample
B; Amount of the N/100 silver nitrate solution used for titration of blank test
S; Amount of sample (g).
The preparation method of an epoxy resin having glycidylamino group, whose hydrolyzable chlorine content is 1000 ppm or less is not especially limited.
For example, the epoxy resin can be obtained by dechlorination and ring-closure reaction of an epoxy resin having glycidylamino group whose hydrolyzable chlorine content is more than 1000 ppm.
Dechlorination reaction is carried out by dissolving an epoxy resin having glycidylamino group in non-protonic polar solvent, and an alkaline substance is added dropwise and retained with stirring.
As an alkaline substance used for this reaction, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. are exemplified, and these are used in the form of aqueous solution or alcoholic solution.
The amount of alkaline substance is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol based on 1 mol of the hydrolyzable chlorine of epoxy resin. When too much amount of alkaline substance is used, polymerization will occur, and when too little, the effect of reduction of hydrolyzable chlorine will become small.
As a non-protonic polar solvent, dimethylsulfoxide, dimethyl sulfone, dimethylacetamide, tetramethylurea, hexamethylphophoramide, etc. are raised, but it is not limited to these.
The amount of non-protonic polar solvent can be used arbitrarily to the amount of epoxy resins, it is suitably 1.0 to 20 times in weight ratio.
Ring-closure reaction is carried out as follows. From the reaction solution obtained above, non-protonic polar solvent contained therein is removed by water-washing or by distillation, and to the solution of the residue whose solvent is replaced with an organic solvent other than non-protonic polar solvent, alkaline substance is added dropwise and stirred, and after the reaction, neutralization is carried out. After then, purification is conducted by partition with water-washing or filtration.
As an alkaline substance used in ring-closure reaction, the same substances used in dechlorination are exemplified.
As organic solvents other than non-protonic polar solvent used in ring-closure reaction, various hydrocarbon solvents and ketone are exemplified, without being limited to these. Among them, ketones such as methylisobutylketone are suitable.
The epoxy resin of the present invention can be used in combination with a curing agent, a curing accelerator, etc. As the curing agent, any curing agent which is usually used as a curing agent for epoxy resins can be used. Examples of the curing agent include dicyandiamide, tetramethylguanidine, polyhydric compounds, acid anhydrides, acid hydrazid compounds, aromatic amines, aliphatic amines and alicyclic amines.
The epoxy resin of the present invention can be used, according to requirements, with adding fillers such as silica, alumina.
Epoxy resin having glycidylamino group with low content of hydrolyzable chlorine of the present invention is useful as electric and electronic materials, such as adhesive, insulating material, and laminated board.
Although concrete examples explain the present invention below, the present invention is not limited to these examples.
Viscosity is measured with using a parallel plate type rheometer (CVO Rheometer, produced by Bohlin Co., Ltd.).
(Preparation of 4-amino-m-cresol Type Epoxy Resin with Low Content of Hydrolyzable Chlorine)
4-amino-m-cresol type epoxy resin having 1450 ppm of hydrolyzable chlorine (comparative example 1, trade name SumiEpoxy ELM-100, Sumitomo Chemical Co.,Ltd.) 60 g was dissolved in dimethylsulfoxide 440 g, and after having replaced the inside of the system with nitrogen, 48% sodium hydroxide aqueous solution 0.35 g (example 1) or 1.27 g (example 2) were added dropwise, respectively, and stirred at 32° C. for 2 hours. After the reaction, neutralization was carried out by adding 0.21 g of phosphoric acid, and 2.4 g of sodium chloride.
(Dechlorination)
Subsequently, dimethyl sulfoxide contained in the above reaction liquid was distilled off under reduced pressure. To residue, methylisobutyl ketone 180 g and 20% hot salt water 80 g were added and partitioned, and then filtrated. The filtrated liquid was washed by hot salt water. (solvent substitution)
Subsequently, 17.2 g of 48% sodium hydroxide aqueous solution was added to the solvent substituted reaction solution, and reaction was carried out at 80° C. for 5 hours. (Ring-closure reaction)
After the reaction, having added carbon dioxide for neutralization, water content was removed by azeotropic dehydration and inorganic content was removed by filtration.
With increasing charged amount of sodium hydroxide in dechlorination, the reduction of hydrolyzable chlorine was confirmed.
TABLE 2 | ||||
Comparative | ||||
Example 1 | Example 2 | example 1 | ||
Charged amount | 0.35 | g | 1.27 | g | — | |
of 48% NaOH | ||||||
Hydrolyzable | 830 | ppm | 660 | ppm | 1450 | ppm |
chlorine | ||||||
Viscosity (25° C.) | 1.7 | Pas | 4.0 | Pas | 1.1 | Pas |
According to the present invention, an epoxy resin having glycidylamino group with low content of hydrolyzable chlorine, which is highly reliable and useful as electric/electronic materials can be provided.
Claims (3)
1. A 4-amino-m-cresol type epoxy resin having a hydrolyzable chlorine content of 1000 ppm or less, wherein said hydrolyzable chlorine is analyzed by a method in which the epoxy resin is dissolved in dioxane and a potassium hydroxide/alcohol solution is added, and the dioxane solution is refluxed for 30 minutes, and a potentiometric titration is conducted using silver nitrate solution.
2. A curable epoxy composition, comprising:
a curing agent; and
an epoxy resin comprising a 4-amino-m-cresol type epoxy resin having a hydrolyzable chlorine content of 1000 ppm or less obtained by a method comprising a dechlorination reaction step wherein a 4-amino-m-cresol type epoxy resin whose hydrolyzable chlorine content is more than 1000 ppm is dissolved in a non-protonic polar solvent, and alkaline substance is added and stirred; and a ring-closure reaction step wherein the non-protonic polar solvent is removed from the above reaction solution by water-washing or by distillation, and to the solution of the residue whose solvent is replaced with an organic solvent other than the protonic polar solvent, alkaline substance is added and stirred; and wherein said hydrolyzable chlorine is analyzed by a method in which the epoxy resin is dissolved in dioxane and a potassium hydroxide/alcohol solution is added, and the dioxane solution is refluxed for 30 minutes, and a potentiometric titration is conducted using silver nitrate solution.
3. A curable epoxy composition according to claim 2 , wherein the curing agent comprises dicyandiamide, tetramethylguanidine, a polyhydric compound, and acid anhydride, an acid hydrazid compound, an aromatic amine, an aliphatic amine, or an alicyclic amine.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14970398 | 1998-05-29 | ||
JP10-149703 | 1998-05-29 |
Publications (2)
Publication Number | Publication Date |
---|---|
US20020177683A1 US20020177683A1 (en) | 2002-11-28 |
US6818727B2 true US6818727B2 (en) | 2004-11-16 |
Family
ID=32260077
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/320,719 Expired - Fee Related US6818727B2 (en) | 1998-05-29 | 1999-05-27 | Highly purified epoxy resin |
Country Status (8)
Country | Link |
---|---|
US (1) | US6818727B2 (en) |
EP (1) | EP0960895B1 (en) |
KR (1) | KR100587743B1 (en) |
CN (1) | CN1237586A (en) |
DE (1) | DE69916698T2 (en) |
MY (1) | MY122050A (en) |
SG (1) | SG103244A1 (en) |
TW (1) | TW593401B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI281478B (en) * | 2000-10-11 | 2007-05-21 | Sumitomo Bakelite Co | Die-attaching paste and semiconductor device |
CN100451080C (en) * | 2004-05-26 | 2009-01-14 | 北京韩创科建筑材料科技有限公司 | Modified double-component epoxy resin paint |
JP2013020947A (en) * | 2011-06-13 | 2013-01-31 | Nitto Denko Corp | Separator for nonaqueous electrolyte power storage device, nonaqueous electrolyte power storage device, and manufacturing methods thereof |
CN104529947A (en) * | 2015-01-12 | 2015-04-22 | 烟台德邦科技有限公司 | Method for reducing chlorinity of epoxy resin reactive diluent |
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JPH0623230B2 (en) * | 1985-08-05 | 1994-03-30 | 住友化学工業株式会社 | Epoxy resin |
JPS63161015A (en) * | 1986-12-25 | 1988-07-04 | Sumitomo Bakelite Co Ltd | Electrically conductive resin paste |
JPH0195150A (en) * | 1987-10-06 | 1989-04-13 | Mitsubishi Rayon Co Ltd | Epoxy resin composition |
JP2627645B2 (en) * | 1988-07-12 | 1997-07-09 | 油化シエルエポキシ株式会社 | Method for producing triglycidyl derivatives of aminophenols |
JPH04139230A (en) * | 1990-10-01 | 1992-05-13 | Sumitomo Metal Ind Ltd | Production of epoxy resin |
EP0700947A3 (en) * | 1994-09-08 | 1996-05-01 | Sumitomo Chemical Co | Epoxy resin composition and resin-encapsulated semiconductor device |
-
1999
- 1999-05-25 MY MYPI99002054A patent/MY122050A/en unknown
- 1999-05-25 TW TW088108554A patent/TW593401B/en not_active IP Right Cessation
- 1999-05-26 SG SG9902584A patent/SG103244A1/en unknown
- 1999-05-27 EP EP99110319A patent/EP0960895B1/en not_active Expired - Fee Related
- 1999-05-27 DE DE69916698T patent/DE69916698T2/en not_active Expired - Fee Related
- 1999-05-27 US US09/320,719 patent/US6818727B2/en not_active Expired - Fee Related
- 1999-05-28 CN CN99107673A patent/CN1237586A/en active Pending
- 1999-05-28 KR KR1019990019493A patent/KR100587743B1/en not_active IP Right Cessation
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US2951825A (en) * | 1958-02-03 | 1960-09-06 | Union Carbide Corp | Glycidyl derivatives of amino phenols |
US4542202A (en) * | 1982-09-21 | 1985-09-17 | Ajinomoto Co., Inc. | Latent curing agents for epoxy resins |
US4487948A (en) | 1983-03-23 | 1984-12-11 | Celanese Corporation | Polyglycidyl hindered aromatic amines |
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EP0193068A1 (en) | 1985-02-18 | 1986-09-03 | Asahi Kasei Kogyo Kabushiki Kaisha | One liquid type epoxy resin composition |
US4900848A (en) | 1985-09-27 | 1990-02-13 | Sumitomo Chemical Company, Limited | Low-viscosity epoxy resin, and fiber-reinforced composite material from triglycidyl m-aminophenols |
US4957995A (en) | 1985-09-27 | 1990-09-18 | Sumitomo Chemical Company, Limited | Low-viscosity epoxy resin, and fiber-reinforced composite material based on m-alkyl triglycidylaminophenols |
US4831101A (en) | 1986-10-28 | 1989-05-16 | Rutgerswerke Ag | Polyglycidyl ethers from purified epihalohydrin |
US5017674A (en) * | 1988-02-05 | 1991-05-21 | Hisashi Tada | Epoxy resin composition for composite material from m- or o-substituted triglycidylaminophenols, with fortifier and latent curing agents |
US5449737A (en) * | 1994-02-11 | 1995-09-12 | Ciba-Geigy Corporation | Urethane modified epoxy resin compositions |
US5545697A (en) | 1994-02-14 | 1996-08-13 | Ciba-Geigy Corporation | Urethane modified epoxy resin compositions |
Also Published As
Publication number | Publication date |
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EP0960895A3 (en) | 2001-01-03 |
SG103244A1 (en) | 2004-04-29 |
MY122050A (en) | 2006-03-31 |
US20020177683A1 (en) | 2002-11-28 |
CN1237586A (en) | 1999-12-08 |
EP0960895B1 (en) | 2004-04-28 |
KR19990088655A (en) | 1999-12-27 |
DE69916698T2 (en) | 2005-04-07 |
DE69916698D1 (en) | 2004-06-03 |
TW593401B (en) | 2004-06-21 |
KR100587743B1 (en) | 2006-06-09 |
EP0960895A2 (en) | 1999-12-01 |
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